CN102030348A - Device and method for continuously preparing magnesium hydroxide flame retardant - Google Patents
Device and method for continuously preparing magnesium hydroxide flame retardant Download PDFInfo
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- CN102030348A CN102030348A CN 201010507480 CN201010507480A CN102030348A CN 102030348 A CN102030348 A CN 102030348A CN 201010507480 CN201010507480 CN 201010507480 CN 201010507480 A CN201010507480 A CN 201010507480A CN 102030348 A CN102030348 A CN 102030348A
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- magnesium
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 title claims abstract description 95
- 239000000347 magnesium hydroxide Substances 0.000 title claims abstract description 90
- 229910001862 magnesium hydroxide Inorganic materials 0.000 title claims abstract description 90
- 239000003063 flame retardant Substances 0.000 title claims abstract description 48
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 239000012066 reaction slurry Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- 230000007306 turnover Effects 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 230000008676 import Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011268 mixed slurry Substances 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000007599 discharging Methods 0.000 abstract description 4
- 230000005484 gravity Effects 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000002431 foraging effect Effects 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 38
- 239000000243 solution Substances 0.000 description 24
- 229910001629 magnesium chloride Inorganic materials 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 15
- 238000002485 combustion reaction Methods 0.000 description 13
- 239000003112 inhibitor Substances 0.000 description 13
- 235000011121 sodium hydroxide Nutrition 0.000 description 13
- 238000012546 transfer Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- 239000012267 brine Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WQVVYEYAFFYPIX-UHFFFAOYSA-N azane;magnesium Chemical compound N.[Mg] WQVVYEYAFFYPIX-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011419 magnesium lime Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a device and method for continuously preparing magnesium hydroxide flame retardant. The device comprises a super gravity reactor unit and one or more serially connected high pressure reactor units, and particularly comprises a super gravity reactor, a stirring tank, a circulating pump, a feeding and discharging heat exchanger, one or more serially connected high pressure reactors and a slurry storing tank. The method comprises the steps of: simultaneously introducing a refining magnesium salt solution a precipitant into the super gravity reactor; mixing with cyclic reaction slurry from the stirring tank for carrying out a precipitation reaction; transporting to the slurry storing tank from a magnesium hydroxide slurry overflow port for aging; pouring the magnesium hydroxide slurry into the feeding and discharging heat exchanger of the high pressure reactor unit to be heated; carrying out continuous hydrothermal treatment in the high pressure reactor; and transporting the last slurry exhausted from the high pressure reactor back into the feeding and discharging heat exchanger to be cooled, and then carrying out post treatment. In the invention, the crystallizing speed and the grain size of the product can be controlled; the product property is good; the energy consumption is greatly reduced; and the carbon emission is decreased.
Description
Technical field
The present invention relates to the preparation of inorganic chemical industry reactor and green inorganic combustion inhibitor magnesium hydroxide, particularly high-gravity technology is used in the inorganic powder preparation process, relates in particular to and adopt serialization hypergravity reaction precipitation and serialization hydrothermal treatment consists technology to produce the flame retardant of magnesium hydroxide novel process.
Background technology
Magnesium hydroxide has decomposition temperature height, Heat stability is good, nontoxic, the smokeless characteristics such as pressing down cigarette that reach, and can be used as the high-performance inorganic fire retardant and is applied in the macromolecular material.Because current environmental requirement is more and more higher, the research of environment amenable fire retardant aspect comes into one's own day by day, makes flame retardant of magnesium hydroxide become the focus of developing at present with research (industrialization) both at home and abroad.Developed country's magnesium hydroxide makes an addition in plastics, the rubber as inorganic combustion inhibitor as " green safety fire retardant " surface treated magnesium hydroxide.50% is inorganic combustion inhibitor in developed country's fire-retardant for plastic, and flame retardant of magnesium hydroxide accounts for 30% of inorganic combustion inhibitor.China's flame retardant of magnesium hydroxide yearly capacity is 1.3 ten thousand t only, and manufacturing enterprise's scale of flame retardant of magnesium hydroxide is a raw material with magnesium chloride, ammonia below 1000t/a, adopt the hydrothermal method explained hereafter, have many defectives such as small scale, energy consumption height, production cost height.Discover that the oxygen index of its flame-retardant polymer system significantly improves when the oxyhydroxide particle diameter that adds is reduced to 1 μ m.Many bibliographical informations are along with particle diameter reduces, and inorganic particulate has the toughness reinforcing effect of enhancing to polymer materials.Therefore, super-refinement becomes an important development direction of flame retardant of magnesium hydroxide, and the superfineization of inorganic combustion inhibitor and rational size distribution research are exactly one of them.The super fine magnesium hydroxide powder can disperse in material well, then can solve the contradiction between Flame Retardancy energy and the mechanical property.Obtaining ultra-fine high dispersing magnesium hydrate flame retardant powder optimal path is to handle by the nano-sized magnesium hydroxide granular precursor being carried out hydro-thermal reaction.Hydro-thermal reaction prepares magnesium hydrate powder, temperature of reaction is generally at 100-300 ℃, pressure is from 0.1MPa-4.0MPa, this method provides a physics that can't obtain, special and a chemical environment under condition of normal pressure for the reaction and the crystallization of precursor, and the process of dissolution-crystallization has been experienced in the formation of powder.Compare with other preparation methods, have crystal grain grow complete, granularity is little, be evenly distributed, particle agglomeration is lighter, advantages such as stoichiometry thing that is easy to get suitable and crystalline form.That is to say, the ultra-fine grain purity height of this method preparation, good dispersity, the crystal degree is good and globule size is controlled.In addition, the inventor finds the aspects such as dispersiveness, purity, particle diameter and size-grade distribution of nano-sized magnesium hydroxide granular precursor in research and production practice, Flame Retardant Magnesium Hydroxide powder characteristic after the hydro-thermal is had very big influence.
The Ministry of Education of Beijing University of Chemical Technology hypergravity Engineering Research Center utilizes high-gravity technology to prepare nanometer, ultra-fine inorganic material powder, obtains good experimental result and industrialization example.The hypergravity environment more much higher that produces during the rotation of hypergravity equipment than earth gravity acceleration, make solution-air, liquid-liquid, liquid-solid two-phase in porous medium, produce the contact of flowing, liquid is torn into the film, silk of nanoscale and drip by great shear forces, produce huge and phase interface fast updating, make the traditional still formula of interphase mass transfer speed ratio, 1～3 order of magnitude of the raising in the tower reactor, microcosmic mixing and mass transfer process are greatly strengthened.Mixing of microcosmic characteristic time t in the hypergravity precipitation reactor
mBe 0.04～0.4ms even littler, and the t in the common stirring-type reactor
mBe 5～50ms, nucleation response feature time t
nBe generally about 1ms.This shows, under the hypergravity environment, can guarantee t
m＜t
n, it is controlled that nucleation process is carried out in microcosmic, uniform environment.At present, the Ministry of Education of Beijing University of Chemical Technology hypergravity Engineering Research Center has utilized this covering device to realize that industrialization production and the annual production of producing ten thousand tons of scale nano-calcium carbonates per year reach 1000 tons of scale high pure and ultra-fine Flame Retardant Magnesium Hydroxide powders.The inventor is under state fund is subsidized (national high-tech research evolutionary operation(EVOP) (863 Program) item number 2002AA302605), adopt high-gravity technology and equipment, carry out the production of magnesium hydroxide flame retardant type powder, with bittern and sodium hydroxide solution in high-gravity rotating bed and stream contact, interphase mass transfer and microcosmic mix greatly to be strengthened, thereby can obtain the very uniform nano-sized magnesium hydroxide precursor of size distribution, median size :≤100nm, thickness 10-30nm handles to nanometer presoma hydrothermal method that to have synthesized granularity little again, sheet, the ultra-fine magnesium hydroxide flame retardant of epigranular and good dispersity.But the complicated energy consumption of existing hydro-thermal reaction method process is big, considers from the angle of industrial application cost, needs further process optimization and technological development.
Summary of the invention
The present invention seeks to provides a lot of innovations and improvement to the production design and the technical elements of flame retardant of magnesium hydroxide, utilizes supergravity reactor to carry out the novel process that continuous precipitation and the continuous hydrothermal treatment consists of single or multiple autoclave prepare flame retardant of magnesium hydroxide.
For achieving the above object, equipment used of the present invention comprises supergravity reactor unit and single or multiple placed in-line autoclaves unit, wherein the supergravity reactor unit comprises supergravity reactor, stirring tank and recycle pump, supergravity reactor is provided with the refined grain magnesium salt import, precipitation agent import and the outlet of reaction mixed slurry, the outlet of reaction mixed slurry is connected with the stirring tank opening for feed by pipeline, the discharge port of stirring tank is connected with supergravity reactor via recycle pump, form circulation loop, stirring tank also is provided with magnesium hydroxide pulp suspension overflow port, and the magnesium hydroxide pulp suspension overflow port of stirring tank is connected with the slurry storage tank by pipeline; The autoclave unit is made up of turnover material interchanger and single or multiple placed in-line autoclave, the slurry storage tank is connected with turnover material interchanger, turnover material interchanger is connected with single or multiple placed in-line successively autoclaves, the discharge port of last step autoclave connects to form the loop with turnover material interchanger and carries out thermal exchange, and the products export of turnover material interchanger is connected with subsequent processing equipment.
Utilize aforesaid device serialization to prepare the method for flame retardant of magnesium hydroxide: refined grain magnesium salt solution and precipitation agent to be fed supergravity reactor simultaneously continuously mix with circulating reaction slurry and carry out precipitin reaction from stirring tank, continuous precipitation prepares the magnesium hydroxide slurry, hypergravity reaction is finished slurry and is delivered to the slurry storage tank from magnesium hydroxide pulp suspension overflow port and carry out ageing, the magnesium hydroxide slurry is heated with the unitary turnover material of high-pressure pump injection autoclave interchanger then, carry out continuous hydrothermal treatment consists at autoclave successively then, after the slurry that the last step autoclave is discharged was got back to once more and imported and exported the material interchanger and lowered the temperature, high dispersive ultra-fine magnesium hydroxide flame retardant powder was prepared in the dry and/or conventional modification of washing after filtration again.Serialization prepares the flame retardant of magnesium hydroxide schema and sees Fig. 1.
Refined grain magnesium salt and precipitation agent are sent into supergravity reactor continuously and are carried out successive reaction, and the reaction paste of employing adjustment simultaneously round-robin mode is controlled the degree of supersaturation in the reaction process, control crystal structure form.The hypergravity reaction is finished slurry and is delivered to the slurry storage tank, delivers to autoclave then and carries out continuous hydrothermal treatment consists, obtains the flame retardant of magnesium hydroxide product through processing such as filtration, washing, drying, modifications then.
This invented technology advantage applies exists:
(1) the employing operate continuously of reaction workshop section can change reaction density and degree of supersaturation by regulating the internal circulating load between charging flow velocity and supergravity reactor and stirring tank, reduce slurry viscosity, thereby realization crystallization rate and product cut size is controlled.Hypergravity successive reaction general flow chart is seen Fig. 2.The hypergravity flow reactor manufactures and designs employing " fixed-rotor reaction device and application thereof " patented technology (patent No.: 01141787.0), fixed-rotor reaction device and present same advantage of hypergravity rotating packed bed, and fixed-the rotor reaction device has different in internal structure with the hypergravity rotating packed bed, because fixed-rotor reaction device is not filled filler, reactant can not stop up bed when operation, do not need frequent cleaning, this is the incomparable advantage of hypergravity rotating packed bed.
(2) hydrothermal treatment consists workshop section adopts continuous hydrothermal treatment consists mode in this technology, and equipment is the operation of single or multiple water heating kettle series connection continuous feeding and discharging material balance.Serialization hydrothermal treatment consists schema is seen Fig. 3.Under this mode is operated, change the mean residence time of slurry by regulating the magnesium hydroxide slurry flow at autoclave, realize that product granularity and flakiness ratio are controlled, rest on water heating kettle magnesium hydroxide particles catalysis the crystalline form of hydrogen in statu nascendi magnesia crystal improve speed, the crystalline flakiness ratio increased, thereby the polarity of magnesium hydrate powder is reduced, improve its dispersiveness, heat decomposition temperature, heat absorption enthalpy in being added into polymer process, more help the performance of its flame retardant properties.
(3) precipitin reaction and hydrothermal treatment consists are carried out continuously, have reduced equipment volume and investment, have improved production efficiency, by improving level of automation, can reduce the influence of human factor to operation;
(4) adopt the serialization hydrothermal treatment consists, import and export the slurry heat exchange, cut down the consumption of energy greatly, reduce carbon emission.
Effect of the present invention:
(1) can change reaction density by the internal circulating load of regulating between supergravity reactor or fixed-rotor reaction device and slurry storage tank, thereby realization crystallization rate and product cut size is controlled;
(2) by changing slurry mean residence time in autoclave, realize that product granularity and flakiness ratio are controlled;
(3) precipitin reaction and hydrothermal treatment consists are carried out continuously, have reduced equipment volume and investment, have improved production efficiency;
(4) adopt the serialization hydrothermal treatment consists, import and export the slurry heat exchange, cut down the consumption of energy greatly, reduce carbon emission;
(5) the Flame Retardant Magnesium Hydroxide product feature of utilizing the present invention and being produced is: magnesium hydroxide master content 〉=98%, iron≤0.05%, calcium≤0.1%, sulfate radical≤0.05%, chlorine root≤0.10%, mean particle size d50=0.5～2.0 micron, d97≤5.0 micron, specific surface BET=1～20m2/g.
Description of drawings
Fig. 1 serialization prepares the flame retardant of magnesium hydroxide schema
Fig. 2 hypergravity successive reaction general flow chart
Wherein 1: supergravity reactor; 2: stirring tank; Flow1: magnesium salt solution import;
Flow2: precipitation agent import; Flow3: reaction mixed slurry;
Flow4: magnesium magma overflow port; P: recycle pump; Cycle: slurry circulation
Fig. 3 serialization hydrothermal treatment consists schema
Slurry wherein: from hypergravity successive reaction magnesium hydroxide particle suspension;
Product: contain magnesium hydroxide fire retardant slurry;
EX: turnover material interchanger;
1,2, N: titanium material high pressure magnetic drives stirring tank;
Fig. 4 embodiment 1 prepared magnesium hydroxide sem analysis
Fig. 5 embodiment 2 prepared magnesium hydroxide sem analysis
Fig. 6 embodiment 3 prepared magnesium hydroxide sem analysis
Fig. 7 embodiment 4 prepared magnesium hydroxide sem analysis
Fig. 8 embodiment 5 prepared magnesium hydroxide sem analysis
Fig. 9 embodiment 6 prepared magnesium hydroxide sem analysis
Figure 10 embodiment 7 prepared magnesium hydroxide sem analysis
Figure 11 embodiment 8 prepared magnesium hydroxide sem analysis
Wherein the A among Fig. 4-Fig. 8 and Figure 11 is a hypergravity successive reaction sample, and B is continuous hydrothermal treatment consists sample, and hypergravity successive reaction sample refers to through the supergravity reactor successive reaction, but without crossing the continuous hydrothermal treatment consists gained of autoclave magnesium hydroxide products.The hydrothermal treatment consists sample is meant through the supergravity reactor successive reaction continuously, passes through the continuous hydrothermal treatment consists gained of autoclave magnesium hydroxide products again.
Embodiment
Embodiment 1:
Prepare flame retardant of magnesium hydroxide continuously with bromine extraction waste brine and ammonia
In bromine extraction waste brine, add the small amount of activated powder after stirring for some time, filtering and removing color and organism obtain as clear as crystal solution, restir adds a spot of yellow soda ash or sodium hydroxide solution is regulated more than the pH value to 5.5, remove de-iron, calcium ion with the accurate filter sediment separate out, obtain limpid colourless purified magnesium chloride solution, dilute with water is configured to the magnesium chloride solution that magnesium ion concentration is 2.0mol/l.After solution is preheated to 30 ℃, with measuring pump delivery in the hypergravity flow reactor, mix with circulation fluid, and react with reverse contact of ammonia, the red-tape operati parameter: the volume ratio of circulation slurry and continuously feeding is that 50: 1,55 ℃ of temperature of reaction, ammonia magnesium mol ratio are 3.5: 1, reaction time 2 hours, the magnesium hydroxide slurry is discharged reactor continuously, enters in the dashpot ageing 1 hour.The magnesium hydroxide slurry is injected continuously first still of four stills series connection hydrothermal reactor with high pressure injection plug pump, 200 ℃ of pressure 1.8MPa of hydrothermal temperature, after 8 hours slurry residence time, discharge from the 4th water heating kettle Continuous Heat Transfer cooling, slurries filtration washing three times, 120 ℃ dry down, prepares the ultra-fine high purity magnesium hydroxide fire retardant of good dispersity powder.With field emission scanning electron microscope to the sample morphology microstructure analysis see Fig. 1, surface-area BET, mean particle size and purity see Table 1, analytical results shows that the product through successive reaction and hydro-thermal is applicable to inorganic combustion inhibitor fully.
Embodiment 2:
With bromine extraction waste brine and ammoniacal liquor is that raw material prepares flame retardant of magnesium hydroxide continuously
With the purified magnesium chloride solution of embodiment 1, dilute with water is configured to the magnesium chloride solution that magnesium ion concentration is 2.6mol/l, and the ammonia of water absorption liquefied ammonia vaporization is configured to the ammoniacal liquor of weight ratio 25%.After magnesium chloride solution and ammoniacal liquor is preheated to 50 ℃, be transported to respectively in the hypergravity flow reactor with volume pump, mix with circulation fluid and to react, the red-tape operati parameter: the volume ratio of circulation slurry and continuously feeding is that 80: 1,55 ℃ of temperature of reaction, ammonia magnesium mol ratio are 3.5: 1, reaction time 1 hour, the magnesium hydroxide slurry is discharged reactor continuously, enters in the dashpot airtight ageing 1 hour.The magnesium hydroxide slurry is injected continuously first still of four stills series connection hydrothermal reactor with high pressure injection plug pump, 200 ℃ of pressure 1.8MPa of hydrothermal temperature, after 6 hours slurry residence time, be cooled to 50 ℃ of discharges from the 4th water heating kettle Continuous Heat Transfer, slurries filtration washing three times, 120 ℃ dry down, prepares the ultra-fine high purity magnesium hydroxide fire retardant of good dispersity powder.With field emission scanning electron microscope to the sample morphology microstructure analysis see Fig. 2, surface-area BET, mean particle size and purity see Table 1, analytical results shows that the product through successive reaction and hydro-thermal is applicable to inorganic combustion inhibitor fully.
Embodiment 3:
With bromine extraction waste brine and milk of lime is that raw material prepares flame retardant of magnesium hydroxide continuously
With the purified magnesium chloride solution of embodiment 1, dilute with water is configured to the magnesium chloride solution that magnesium ion concentration is 2.2mol/l, and the preparing quick lime piece joins in 90 ℃ of deionized waters, stir digestion 1 hour, 200 mesh sieve are crossed in ageing under the room temperature, make the Ca that solid content is 8.0%～13.0% (w) (OH)
2Suspension.After magnesium chloride solution and milk of lime is preheated to 80 ℃, be transported to respectively in the hypergravity flow reactor with volume pump, mix with circulation fluid and to react, the red-tape operati parameter: the volume ratio of circulation slurry and continuously feeding is that 80: 1,80 ℃ of temperature of reaction, calcium magnesium mol ratio are 0.9: 1, reaction time 2 hours, the magnesium hydroxide slurry is discharged reactor continuously, enters in the dashpot airtight ageing 1 hour.The magnesium hydroxide slurry is injected continuously first still of four stills series connection hydrothermal reactor with high pressure injection plug pump, 210 ℃ of pressure 1.6MPa of hydrothermal temperature, after 10 hours slurry residence time, be cooled to 80 ℃ of discharges from the 4th water heating kettle Continuous Heat Transfer, slurries filtration washing three times, 120 ℃ dry down, prepares the low flame retardant of magnesium hydroxide powder of the ultra-fine calcic of good dispersity.With field emission scanning electron microscope to the sample morphology microstructure analysis see Fig. 3, surface-area BET, mean particle size and purity see Table 1, analytical results shows that the product through successive reaction and hydro-thermal is applicable to inorganic combustion inhibitor fully.
Embodiment 4:
With salt lake crystal magnesium and milk of lime is that raw material prepares flame retardant of magnesium hydroxide continuously
Add water-solubleization salt lake crystal magnesium chloride, stirring a spot of yellow soda ash of adding or sodium hydroxide solution regulates more than the pH value to 7, remove de-iron, calcium ion with the accurate filter sediment separate out, obtain the water white transparency magnesium chloride solution, dilute with water is configured to the magnesium chloride solution that magnesium ion concentration is 2.2mol/l, and the preparing quick lime piece joins in 90 ℃ of deionized waters, stir digestion 1 hour, 200 mesh sieve are crossed in ageing under the room temperature, system
Fig. 3, embodiment 3 usefulness bromine extraction waste brines and milk of lime prepare the magnesium hydroxide sem analysis continuously, and to become solid content be the Ca (OH) of 8.0%～13.0% (w)
2Suspension.After magnesium chloride solution and milk of lime is preheated to 80 ℃, be transported to respectively in the hypergravity flow reactor with volume pump, mix with circulation fluid and to react, the red-tape operati parameter: the volume ratio of circulation slurry and continuously feeding is that 80: 1,80 ℃ of temperature of reaction, calcium magnesium mol ratio are 0.9: 1, reaction time 2 hours, the magnesium hydroxide slurry is discharged reactor continuously, enters in the dashpot airtight ageing 1 hour.The magnesium hydroxide slurry is injected continuously first still of four stills series connection hydrothermal reactor with high pressure injection plug pump, 210 ℃ of pressure 1.6MPa of hydrothermal temperature, after 10 hours slurry residence time, be cooled to 80 ℃ of discharges from the 4th water heating kettle Continuous Heat Transfer, slurries filtration washing three times, 120 ℃ dry down, prepares the low flame retardant of magnesium hydroxide powder of the ultra-fine calcic of good dispersity.With field emission scanning electron microscope to the sample morphology microstructure analysis see Fig. 3, surface-area BET, mean particle size and purity see Table 1, analytical results shows that the product through successive reaction and hydro-thermal is applicable to inorganic combustion inhibitor fully.
Embodiment 5:
With bromine extraction waste brine and liquid caustic soda is that raw material prepares flame retardant of magnesium hydroxide continuously
With the purified magnesium chloride solution of embodiment 1, dilute with water is configured to the magnesium chloride solution that magnesium ion concentration is 2.8mol/l, and the liquid caustic soda with 33% is diluted to the 6mol/l sodium hydroxide solution.After magnesium chloride and sodium hydroxide solution be preheated to 50 ℃, be transported to respectively in the hypergravity flow reactor with volume pump, mix with circulation fluid and to react, the red-tape operati parameter: the volume ratio of circulation slurry and continuously feeding is that 100: 1,55 ℃ of temperature of reaction, alkali magnesium mol ratio are 2.4: 1, reaction time 2 hours, the magnesium hydroxide slurry is discharged reactor continuously, enters in the dashpot ageing 1 hour.The magnesium hydroxide slurry is injected single still hydrothermal reactor continuously with high pressure injection plug pump, 215 ℃ of hydrothermal temperatures, pressure 1.75MPa, after 6 hours slurry residence time, be cooled to 50 ℃ of discharges from the water heating kettle Continuous Heat Transfer, slurries filtration washing three times, 120 ℃ dry down, prepares the ultra-fine high purity magnesium hydroxide fire retardant of good dispersity powder.With field emission scanning electron microscope to the sample morphology microstructure analysis see Fig. 2, surface-area BET, mean particle size and purity see Table 2, analytical results shows that the product through successive reaction and hydro-thermal is applicable to inorganic combustion inhibitor fully.
Embodiment 6:
With bromine extraction waste brine and liquid caustic soda is that raw material prepares flame retardant of magnesium hydroxide continuously
The magnesium hydroxide slurry of embodiment 5 is injected continuously first still of four stills series connection hydrothermal reactor with high pressure injection plug pump, 180 ℃ of pressure 1.3MPa of hydrothermal temperature, after 6 hours slurry residence time, be cooled to 80 ℃ of discharges from the 4th water heating kettle Continuous Heat Transfer, slurries filtration washing three times, 120 ℃ dry down, prepares the ultra-fine high-purity flame retardant of magnesium hydroxide powder of good dispersity.With field emission scanning electron microscope to the sample morphology microstructure analysis see Fig. 6, surface-area BET, mean particle size and purity see Table 2, analytical results shows that the product through successive reaction and hydro-thermal is applicable to inorganic combustion inhibitor fully.
Embodiment 7:
With bromine extraction waste brine and liquid caustic soda is that raw material prepares flame retardant of magnesium hydroxide continuously
The magnesium hydroxide slurry of embodiment 5 is injected continuously first still of four stills series connection hydrothermal reactor with high pressure injection plug pump, 200 ℃ of pressure 1.45MPa of hydrothermal temperature, after about 8 hours slurry residence time, be cooled to 80 ℃ of discharges from the 4th water heating kettle Continuous Heat Transfer, slurries filtration washing three times, 120 ℃ dry down, prepares the ultra-fine high-purity flame retardant of magnesium hydroxide powder of good dispersity.With field emission scanning electron microscope to the sample morphology microstructure analysis see Fig. 6, surface-area BET, mean particle size and purity see Table 2, analytical results shows that the product through successive reaction and hydro-thermal is applicable to inorganic combustion inhibitor fully.
Embodiment 8:
With bromine extraction waste brine and liquid caustic soda is that raw material prepares flame retardant of magnesium hydroxide continuously
With the purified magnesium chloride solution of embodiment 1, dilute with water is configured to the magnesium chloride solution that magnesium ion concentration is 2.8mol/l, and the liquid caustic soda with 33% is diluted to the 6mol/l sodium hydroxide solution.After magnesium chloride and sodium hydroxide solution be preheated to 100 ℃, be transported to respectively in the hypergravity flow reactor with volume pump, mix with circulation fluid and to react, the red-tape operati parameter: the volume ratio of circulation slurry and continuously feeding is that 80: 1,120 ℃ of temperature of reaction, alkali magnesium mol ratio are 2.2: 1, reaction time 2 hours, the magnesium hydroxide slurry is discharged reactor continuously, enters in the slurry storage tank ageing 1 hour.The magnesium hydroxide slurry injects first still of four stills series connection hydrothermal reactor continuously with high pressure injection plug pump, 200 ℃ of pressure 1.3MPa of hydrothermal temperature, after 4 hours slurry residence time, be cooled to 80 ℃ of discharges from the 4th water heating kettle Continuous Heat Transfer, slurries filtration washing three times, 120 ℃ dry down, prepares the ultra-fine high-purity flame retardant of magnesium hydroxide powder of good dispersity.With field emission scanning electron microscope to the sample morphology microstructure analysis see Fig. 7, surface-area BET, mean particle size and purity see Table 2.Analytical results shows that the product through successive reaction and hydro-thermal is applicable to inorganic combustion inhibitor fully.
The magnesium hydrate powder physical and chemical index is analyzed before and after the table 1. embodiment 1-4 hydro-thermal
The magnesium hydrate powder physical and chemical index is analyzed before and after the table 2. embodiment 5-8 hydro-thermal
Claims (2)
1. a serialization prepares flame retardant of magnesium hydroxide equipment, it is characterized in that, comprise supergravity reactor unit and single or multiple placed in-line autoclaves unit, wherein the supergravity reactor unit comprises supergravity reactor, stirring tank and recycle pump, supergravity reactor is provided with the refined grain magnesium salt import, precipitation agent import and the outlet of reaction mixed slurry, the outlet of reaction mixed slurry is connected with the stirring tank opening for feed by pipeline, the discharge port of stirring tank is connected with supergravity reactor via recycle pump, form circulation loop, stirring tank also is provided with magnesium hydroxide pulp suspension overflow port, and the magnesium hydroxide pulp suspension overflow port of stirring tank is connected with the slurry storage tank by pipeline; The autoclave unit is made up of turnover material interchanger and single or multiple placed in-line autoclave, the slurry storage tank is connected with turnover material interchanger by pump, turnover material interchanger is connected with single or multiple placed in-line successively autoclaves, the discharge port of last step autoclave connects to form the loop with turnover material interchanger and carries out thermal exchange, and the products export of turnover material interchanger is connected with subsequent processing equipment.
2. utilize the equipment serialization of claim 1 to prepare the method for flame retardant of magnesium hydroxide, it is characterized in that, may further comprise the steps: refined grain magnesium salt solution and precipitation agent are fed supergravity reactor simultaneously continuously, mix with circulating reaction slurry and to carry out precipitin reaction from stirring tank, continuous precipitation prepares the magnesium hydroxide slurry, hypergravity reaction is finished slurry and is delivered to the slurry storage tank from magnesium hydroxide pulp suspension overflow port and carry out ageing, the magnesium hydroxide slurry injects the unitary turnover material of autoclave interchanger with high-pressure pump and is heated, carry out continuous hydrothermal treatment consists at autoclave successively then, after the slurry that the last step autoclave is discharged was got back to once more and imported and exported the material interchanger and lowered the temperature, washing was dry after filtration again, high dispersive ultra-fine magnesium hydroxide flame retardant powder is prepared in conventional modification.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130250A (en) * | 2011-11-22 | 2013-06-05 | 北京化工大学 | Method for preparing active magnesium oxide |
| CN104437287A (en) * | 2013-09-18 | 2015-03-25 | 郑莹 | Reaction apparatus |
| CN106629791A (en) * | 2016-10-11 | 2017-05-10 | 中北大学 | Device and process for synthesizing superfine magnesium hydroxide flame retardant based on supergravity-crystal seed method |
| CN108640677A (en) * | 2018-06-22 | 2018-10-12 | 万华化学集团股份有限公司 | A kind of nano composite oxides zirconium powder preparation that crystallite dimension is controllable |
| CN108707755A (en) * | 2018-09-05 | 2018-10-26 | 成都天智轻量化科技有限公司 | The system and its extracting method of extraction of metal magnesium in a kind of raffinate from sea water desalination |
| CN108905895A (en) * | 2018-06-06 | 2018-11-30 | 浙江海洋大学 | A kind of quick hydrothermal synthesis device and method |
| CN112239222A (en) * | 2019-07-18 | 2021-01-19 | 自然资源部天津海水淡化与综合利用研究所 | Equipment and method for continuous hydrothermal production of magnesium hydroxide |
| CN115417436A (en) * | 2022-09-20 | 2022-12-02 | 西部金属材料股份有限公司 | Preparation method of two-dimensional magnesium hydroxide nanosheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103130250A (en) * | 2011-11-22 | 2013-06-05 | 北京化工大学 | Method for preparing active magnesium oxide |
| CN103130250B (en) * | 2011-11-22 | 2014-12-03 | 北京化工大学 | Method for preparing active magnesium oxide |
| CN104437287A (en) * | 2013-09-18 | 2015-03-25 | 郑莹 | Reaction apparatus |
| CN106629791A (en) * | 2016-10-11 | 2017-05-10 | 中北大学 | Device and process for synthesizing superfine magnesium hydroxide flame retardant based on supergravity-crystal seed method |
| CN106629791B (en) * | 2016-10-11 | 2018-04-27 | 中北大学 | The device and technique of a kind of hypergravity-crystal seed method synthesizing superfine flame retardant of magnesium hydroxide |
| CN108905895A (en) * | 2018-06-06 | 2018-11-30 | 浙江海洋大学 | A kind of quick hydrothermal synthesis device and method |
| CN108640677A (en) * | 2018-06-22 | 2018-10-12 | 万华化学集团股份有限公司 | A kind of nano composite oxides zirconium powder preparation that crystallite dimension is controllable |
| CN108707755A (en) * | 2018-09-05 | 2018-10-26 | 成都天智轻量化科技有限公司 | The system and its extracting method of extraction of metal magnesium in a kind of raffinate from sea water desalination |
| CN108707755B (en) * | 2018-09-05 | 2023-05-30 | 成都天智轻量化科技有限公司 | System and method for extracting magnesium metal from seawater desalination raffinate |
| CN112239222A (en) * | 2019-07-18 | 2021-01-19 | 自然资源部天津海水淡化与综合利用研究所 | Equipment and method for continuous hydrothermal production of magnesium hydroxide |
| CN115417436A (en) * | 2022-09-20 | 2022-12-02 | 西部金属材料股份有限公司 | Preparation method of two-dimensional magnesium hydroxide nanosheet |
| CN115417436B (en) * | 2022-09-20 | 2023-08-11 | 西部金属材料股份有限公司 | Preparation method of two-dimensional magnesium hydroxide nano-sheet |
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